CN107438484B - Sodium polyphosphate supported catalyst with improved activity and method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol by using same - Google Patents
Sodium polyphosphate supported catalyst with improved activity and method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol by using same Download PDFInfo
- Publication number
- CN107438484B CN107438484B CN201680020546.0A CN201680020546A CN107438484B CN 107438484 B CN107438484 B CN 107438484B CN 201680020546 A CN201680020546 A CN 201680020546A CN 107438484 B CN107438484 B CN 107438484B
- Authority
- CN
- China
- Prior art keywords
- butadiene
- butanediol
- methyl ethyl
- ethyl ketone
- supported catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/12—Alkadienes
- C07C11/16—Alkadienes with four carbon atoms
- C07C11/167—1, 3-Butadiene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/10—Methyl-ethyl ketone
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a sodium polyphosphate supported catalyst having improved activity and a method for preparing methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol using the same, and more particularly, to a sodium polyphosphate supported catalyst in which a compound having a polyphosphate structure prepared by a condensation reaction of a sodium phosphate precursor is supported in a catalyst carrier and a method for preparing methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol with high yield using the same and capable of improving the selectivity of 1, 3-butadiene.
Description
Technical Field
The present invention relates to a sodium polyphosphate supported catalyst having improved activity and a method for preparing methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol using the same, and more particularly, to a sodium polyphosphate supported catalyst in which a compound having a polyphosphate structure prepared by a condensation reaction of a sodium phosphate precursor is supported in a catalyst carrier and a method for preparing methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol with high yield and increasing the selectivity of 1,3-butadiene using the same.
Background
2,3-butanediol (2,3-butanediol) as an example of a compound that can be produced from biomass as a clean resource, 2,3-butanediol was produced by fermentation of xylose (xylose) and glucose (glucose) in kanden (Harden) and wooll (Walpole) in 1906, and then, it was actively studied to produce it using biotechnology.
In particular, since 2,3-butanediol is used as a precursor of various compounds such as synthetic rubber, plasticizer, antifreeze, fuel additive, etc., it is expected that the production of 2,3-butanediol by bioengineering will continue to increase, and the demand relating to a technique for more valuable utilization thereof will also become high.
1,3-butadiene (1,3-butadiene) is a core material of industrial raw materials used for manufacturing automobile parts such as tires and fuel lines, shoes, parts of electronic products, and the like, and is a representative chemical product with a world market size of 1 million tons/year and 22 million won/year. Commercial production of 1,3-butadiene is achieved by a process of extracting and purifying byproducts of an ethylene production process produced by steam cracking, and 1,3-butadiene is partially obtained by dehydrogenation of n-butane (n-butane) or n-butene (nbutene). Since 1,3-butadiene is obtained as a by-product of ethylene production, the amount of 1,3-butadiene produced is linked to the amount of ethylene produced, and it is difficult to adjust the amount of butadiene produced according to market conditions.
Methyl Ethyl Ketone (MEK) is a representative solvent used in many process fields, but it is not produced in korea, and thus it is totally imported. In particular, methyl ethyl ketone is not only used as a solvent for nitrocellulose (nitrocellulose), vinyl resin, cellulose acetate, and the like, but is consumed in many industrial fields such as polyurethane, paint, magnetic tape, ink, synthetic leather, adhesive, coating agent, and the like.
A conventional process for producing the methyl ethyl ketone involves dehydrogenation of 2-butanol (2-butanol) obtained by hydration (hydration) of 1-butene (1-butene) or 2-butene (2-butene) as a C4 fraction of naphtha to produce methyl ethyl ketone under conditions of a high temperature of 400 to 500 ℃ and a high pressure of about 4bar using a zinc (Zn), copper (Cu) or tin (Sn) catalyst.
However, the oil prices are continuously kept high all over the world, and the demand for the C4 fraction for olefin production or ethylene decomposition increases, so that there are many inconveniences in the supply of raw materials, and price instability continues.
2,3-butanediol can be converted to methyl ethyl ketone and 1,3-butadiene by a dehydration reaction (dehydration) which requires a dehydration catalyst. It is known that homogeneous inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid exhibit high activity in dehydration of 2,3-butanediol, but corrode a reactor, are difficult to handle, and it takes much time and cost to separate them from the product.
In connection with this, a process using a lithium phosphate-based catalyst in the dehydration of vicinal diol (vicinal diol) to a diene is disclosed in U.S. Pat. No. 5,245,798, but the degree of selectivity of 1,3-butadiene is not high.
Therefore, in order to efficiently produce methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol, it is still necessary to develop a catalyst which can be easily separated from the product and has high activity.
Disclosure of Invention
Technical problem to be solved by the invention
In view of the above, the present inventors have made studies and efforts to develop a new form of catalyst having high activity in the process of preparing methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol, and finally have found that a sodium polyphosphate supported catalyst in which a compound having a polyphosphate structure prepared by a condensation reaction of a sodium phosphate precursor is supported on a catalyst carrier can produce methyl ethyl ketone and 1,3-butadiene in high yield, and particularly, can greatly improve the selectivity of 1,3-butadiene, thereby completing the present invention.
Accordingly, an object of the present invention is to provide a sodium polyphosphate supported catalyst in which a compound having a polyphosphate structure prepared by a condensation reaction of a sodium phosphate precursor is supported in a catalyst carrier, a method for preparing the catalyst, and a method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol using the catalyst.
Technical scheme
The present invention is characterized in that a polyphosphate structural compound prepared by a condensation reaction of a sodium phosphate precursor is a sodium polyphosphate supported catalyst supported in a catalyst carrier.
In addition, another feature of the present invention is to provide a method for preparing a sodium polyphosphate supported catalyst, the method comprising: a step of dissolving a sodium phosphate precursor in water to prepare a first precursor solution; mixing Na2HPO4Or a step of dissolving NaOH in water to prepare a second precursor solution; and a step of separating a precipitate generated by mixing the first precursor solution and the second precursor solution with the catalyst carrier, and drying, granulating, and calcining the precipitate to prepare a supported catalyst.
Another aspect of the present invention is to provide a method for preparing methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol, the method for preparing methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol comprising: a step of obtaining a gasified product by gasifying 2, 3-butanediol; and a step of reacting the vapor with the sodium polyphosphate supported catalyst described above.
Advantageous effects
The sodium polyphosphate supported catalyst of the present invention is structurally stabilized by having a polyphosphate structure, and thus the stability of the catalyst is improved as compared to a lithium phosphate supported catalyst.
Compared with the lithium phosphate supported catalyst, the sodium polyphosphate supported catalyst provided by the invention has the advantages that the raw material cost is reduced, and the economic benefit is improved.
When the sodium polyphosphate-supported catalyst of the present invention is used in a process for producing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol, the yield of 1,3-butadiene is greatly improved, the stability of the catalyst is improved, and the phenomenon of deactivation over time can be prevented.
In addition, the sodium polyphosphate supported catalyst of the present invention can improve the selectivity of 1,3-butadiene, and thus can be widely applied to the preparation of 1,3-butadiene, which is an industrial raw material for automobile parts, shoes, electronic products, and the like.
Drawings
FIG. 1 shows a schematic of a continuous gas phase reaction for the production of methyl ethyl ketone and 1,3-butadiene from 2, 3-butanediol.
FIG. 2 is a graph showing the results of a reaction for producing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol using the catalyst in example 1 and the catalyst in comparative example 1, in which the ratio (ratio) of 1,3-butadiene to methyl ethyl ketone based on the operating time is determined.
Detailed Description
The advantages and features of the present invention and methods of accomplishing the same will become apparent with reference to the detailed description of the embodiments that follow. However, the present invention is not limited to the embodiments disclosed below, and can be embodied in various forms different from each other, and the embodiments are only for making the disclosure of the present invention more complete, and to fully inform the scope of the present invention to those skilled in the art to which the present invention pertains, and the present invention is defined only by the scope of the claims.
The sodium polyphosphate-supported catalyst of the present invention, the method for preparing the catalyst, and the method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol using the catalyst will be described in detail below.
Sodium polyphosphate supported catalyst
A compound having a polyphosphate structure prepared by a condensation reaction of a sodium phosphate precursor is supported on a catalyst support, thereby preparing the sodium polyphosphate supported catalyst of the present invention.
The sodium phosphate precursor undergoes a condensation reaction in an aqueous solution as represented by the following formula 1.
Formula 1:
that is, a compound forming a polyphosphate structure, and thus catalyst stability is significantly improved.
In this case, Na may be mixed in the sodium phosphate precursor forming the polyphosphate structure2HPO4Or NaOH precursor, the chain length is adjusted by capping the compound of the above polyphosphate structure as shown in the following formula 2.
Formula 2:
that is, the sodium polyphosphate supported catalyst of the present invention is characterized by comprising the above sodium phosphate precursor and Na mixed together2HPO4Or NaOH precursor, to allow a compound having a polyphosphate structure including a structure of the following chemical formula 1 with a chain length adjusted to be supported in the catalyst support.
Chemical formula 1:
wherein n is more than or equal to 2 and less than or equal to 10.
In the present invention, a preferable example of the substance for adjusting the chain length of the condensation reaction of the sodium phosphate precursor is Na2HPO4Or NaOH, but is not limited thereto.
Preferably, in the present invention, the above Na2HPO4And sodium phosphate precursor at a molar ratio of 2:0.3 to 1, more preferably, Na as described above2HPO4And sodium phosphate precursorThe molar ratio of (A) to (B) is 2:0.38 to 1, and particularly preferably 2:0.38 to 0.44. Within the above range, the reactivity can be achieved at a level of about 2.0 or more in the ratio of 1, 3-butadiene/methyl ethyl ketone (ratio), 100% in conversion ratio, and about 90% or more in the selectivity of 1,3-butadiene and methyl ethyl ketone.
Preferably, in the present invention, the molar ratio of the NaOH and the sodium phosphate precursor is 2:2 to 3, and more preferably, the molar ratio of the NaOH and the sodium phosphate precursor is 2:2 to 2.44. Within the above range, the reactivity can be achieved at a level of about 2.0 or more in the ratio of 1, 3-butadiene/methyl ethyl ketone, 100% in conversion ratio, and about 90% or more in the selectivity of 1,3-butadiene and methyl ethyl ketone.
In the present invention, the catalyst support may be one or a mixture of two or more selected from the group consisting of silica, alumina, γ -alumina, zirconia, titania, and silica-alumina, but is not limited thereto, and preferably may be silica.
The sodium polyphosphate supported catalyst is used in the process of preparing methyl ethyl ketone and 1,3-butadiene by using 2, 3-butanediol.
Preparation method of sodium polyphosphate supported catalyst
The preparation method of the sodium polyphosphate supported catalyst comprises the following steps.
Step a), a sodium phosphate precursor is dissolved in water to prepare a first precursor solution.
Step b), adding Na2HPO4Or NaOH dissolved in water to prepare a second precursor solution.
And c) separating precipitates formed by mixing the first precursor solution and the second precursor solution with a catalyst carrier, and drying, granulating and calcining the precipitates to prepare the sodium polyphosphate supported catalyst.
As described above, the catalyst support may be one or a mixture of two or more selected from the group consisting of silica, alumina, γ -alumina, zirconia, titania, and silica-alumina, but is not limited thereto, and preferably silica is used.
That is, the sodium polyphosphate supported catalyst of the present invention can be prepared by the following routes of formula 3 and formula 4.
Formula 3:
3NaH2PO4+2NaOH+SiO2→Na5P3O10/SiO2+4H2O
formula 4:
NaH2PO4+2Na2HPO4+SiO2→Na5P3O10/SiO2+2H2O
among them, Na in the above-mentioned second precursor solution is preferable2HPO4And the molar ratio of the sodium phosphate precursor in the first precursor solution is 2: 0.3-1, and the molar ratio of the NaOH in the second precursor solution to the sodium phosphate precursor in the first precursor solution is 2: 2-3. The reason for this is as described above.
Preferably, in the preparation of the sodium polyphosphate supported catalyst, the calcination process is performed at a temperature of 400 to 700 ℃, more preferably, at a temperature of 450 to 600 ℃. Also, the above calcination process may be performed for about 1 to 5 hours.
In the preparation of the catalyst through the above process, by-products other than water are not produced, and thus, a sodium polyphosphate supported catalyst having improved stability can be prepared even without additional filtering and pulverizing processes.
Preparation method of methyl ethyl ketone and 1,3-butadiene
The method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol using the catalyst of the present invention is characterized by comprising the following steps.
A step of obtaining a gasified product by gasifying 2, 3-butanediol.
And a step of reacting the vapor with the prepared sodium polyphosphate supported catalyst.
In this case, an inert gas may be mixed with the 2,3-butanediol vapor to form a mixture, and then the mixture may be reacted with the prepared sodium polyphosphate supported catalyst.
FIG. 1 shows a scheme for the preparation of Methyl Ethyl Ketone (MEK) and 1,3-butadiene (C) using 2,3-butanediol4H6) Schematic diagram of a continuous gas phase reaction.
As shown in FIG. 1, 2,3-butanediol can be converted to methyl ethyl ketone and 1,3-butadiene by a continuous gas phase reaction. Specifically, a 2,3-butanediol solution is injected into an evaporation zone (evaporation zone) at a predetermined rate by a pump. Preferably, the evaporation area is maintained at a temperature of 200 to 250 ℃ so that the 2,3-butanediol is completely vaporized.
The reaction is carried out by supplying 2,3-butanediol vapor vaporized in the evaporation region or a mixed gas in which an inert gas such as nitrogen, helium or argon is mixed into the 2,3-butanediol vapor from the upper part to the lower part of a stainless steel (stainless steel) reactor or a quartz (quartz) reactor, through a catalyst layer containing the sodium polyphosphate supported catalyst of the present invention.
In this case, the sodium polyphosphate supported catalyst is preferably used by activating it at a high temperature under nitrogen conditions, and more preferably activated at a temperature of 300 to 600 ℃.
On the other hand, it is preferable that the temperature range of the reaction in which 2,3-butanediol passes through the catalyst layer is 300 to 500 ℃, and if the reaction temperature is less than 300 ℃, the activity is low, and if the reaction temperature is more than 500 ℃, the energy consumption is large, the economical efficiency is lowered, and the aging phenomenon of the catalyst is accelerated by the over-reaction. The reaction pressure may be normal pressure (about 1 atm), but is not particularly limited.
In the method for preparing methyl ethyl ketone and 1,3-butadiene by using 2,3-butanediol, the person skilled in the art can use Gas Hourly Space Velocity (GHSV) of 1-1000 hrs-1Is adjusted and operated within the range of conditions of (1).
Hereinafter, a method for preparing the sodium polyphosphate-supported catalyst of the present invention and a method for preparing methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol using the same will be described in detail with reference to preferred examples of the present invention and comparative examples.
The following examples and comparative examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.
1. Preparation example
Preparation examples 1 to 5
Sodium phosphate (NaH)2PO4) Dissolving the precursor in water to prepare a first precursor solution (0.1-5 mol), and adding Na2HPO4The second precursor solution (0.5 to 1.5mol) is prepared by dissolving in water, and then the first precursor solution (0.5 to 2ml) and the second precursor solution (0 to 20ml) are mixed together with 5 to 15g of silica gel. The obtained mixture was dried at a temperature of 100 ℃ to remove water and separate the resulting precipitate (Na)2HPO4:NaH2PO42: 0.38-2). Next, the separated precipitate in a powder state is subjected to a forming operation (granulation) of a specific form, and is calcined at a temperature of 400 to 500 ℃, thereby preparing a sodium polyphosphate supported catalyst having a weight percentage of about 25%.
In this case, the above Na is shown in Table 1 below2HPO4And sodium phosphate (NaH)2PO4) The molar ratios of the components were varied to prepare sodium polyphosphate supported catalysts of preparation examples 1 to 5.
TABLE 1
Preparation examples 6 to 9
Sodium phosphate (NaH)2PO4) A first precursor solution (1 to 3mol) is prepared by dissolving a precursor in water, a second precursor solution (1.8 to 3mol) is prepared by dissolving NaOH in water, and then 5 to 10ml of the first precursor solution and 5 to 10ml of the second precursor solution are mixed together with 5 to 15g of silica gel. The resulting mixture was dried at a temperature of 100 ℃ to remove water and separate the resulting precipitate (NaOH: NaH)2PO42: 1-3). Subsequently, the separated precipitate in the form of powder is passed throughThe catalyst is prepared by forming (granulating) a specific form and calcining the formed product at a temperature of 400 to 500 ℃ to obtain a sodium polyphosphate supported catalyst with a weight percentage of about 25%.
At this time, the above NaOH and sodium phosphate (NaH) were used as shown in Table 2 below2PO4) The molar ratios of the components were varied to prepare sodium polyphosphate supported catalysts of preparation examples 6 to 9.
TABLE 2
Evaluation of catalyst Performance in 2,3-butanediol dehydration reaction
Examples 1 to 9
The steps shown in fig. 1, i.e., the reactions for producing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol were performed using the sodium polyphosphate supported catalysts obtained in production examples 1 to 9, respectively, and specific reaction conditions are shown in table 3.
TABLE 3
| Amount of catalyst | 5g |
| Reaction temperature | 400℃ |
| Amount of reactant supplied | 5 ml/min |
| Nitrogen (N)2) Amount of |
100 ml/min |
Comparative example 1
The reaction was carried out under the same conditions as in example 1, using Li as a catalyst3PO4Instead of the sodium polyphosphate supported catalyst obtained in preparation examples 1 to 9.
Comparative example 2
The reaction was carried out under the same conditions as in example 1, using Na as a catalyst2HPO4Instead of the sodium polyphosphate supported catalyst obtained in preparation examples 1 to 9.
Results of Performance evaluation
The performance results of the catalysts based on the above examples and comparative examples are shown in the following table 4.
TABLE 4
Then, according to example 1 and comparative example 1, the reaction for producing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol was carried out, and the value of the ratio of 1, 3-butadiene/methyl ethyl ketone (ratio) based on the operating time (h) was obtained and the results thereof are shown in a graph (fig. 2).
From the results shown in table 4 and fig. 2, it is confirmed that the sodium polyphosphate supported catalyst according to the present invention has excellent stability, and thus can improve the conversion ratio of 1, 3-butadiene/methyl ethyl ketone using 2,3-butanediol and the selectivity of 1, 3-butadiene/methyl ethyl ketone, and particularly, can greatly improve the productivity of 1,3-butadiene as compared with the conventional catalyst.
While the embodiments of the present invention have been described above, the embodiments are merely examples, and those skilled in the art to which the present invention pertains will appreciate that various modifications and other embodiments can be made. Therefore, the true technical scope of the present invention should be judged by the claims.
Claims (7)
1. A method for preparing methyl ethyl ketone and 1,3-butadiene by using 2,3-butanediol is characterized in that,
a step of obtaining a gasified product by gasifying 2, 3-butanediol; and
a step of reacting the vapor with a sodium polyphosphate supported catalyst,
wherein the sodium polyphosphate supported catalyst is prepared by supporting a compound having a polyphosphate structure prepared by a condensation reaction of a sodium phosphate precursor in a catalyst carrier,
the compound having a polyphosphate structure has a structure of the following chemical formula 1,
chemical formula 1:
wherein n satisfies the following condition: n is more than or equal to 3 and less than or equal to 10.
2. The method of claim 1, wherein the condensation reaction of the sodium phosphate precursor with Na is performed by using 2,3-butanediol to prepare methyl ethyl ketone and 1,3-butadiene2HPO4Or NaOH to adjust the chain length.
3. The method for producing methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol as claimed in claim 2, wherein Na is contained in the above-mentioned solution2HPO4And the molar ratio of the sodium phosphate precursor to the sodium phosphate precursor is 2: 0.3-1.
4. The method of claim 2, 3-butanediol-based production of methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol, wherein the molar ratio of the NaOH to the sodium phosphate precursor is 2:2 to 3.
5. The method of claim 1, wherein the catalyst support is one or a mixture of two or more selected from the group consisting of silica, alumina, zirconia, titania and silica-alumina.
6. The method for preparing methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol according to claim 1, wherein the vapor is mixed with an inert gas and then reacted with the sodium polyphosphate supported catalyst.
7. The method for producing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol according to claim 1, wherein the reaction between the vapor and the sodium polyphosphate supported catalyst is carried out at a temperature of 300 to 500 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150046430A KR101706449B1 (en) | 2015-04-01 | 2015-04-01 | Poly Sodium phosphate supported catalyst with improved activity and method of preparing methylethylketone and 1,3-butadiene from 2,3-butanediol using the same |
| KR10-2015-0046430 | 2015-04-01 | ||
| PCT/KR2016/003249 WO2016159650A1 (en) | 2015-04-01 | 2016-03-30 | Poly(sodium phosphate) supported catalyst having improved activity, and method wherein methyl ethyl ketone and 1,3-butadiene are produced from 2,3-butanediol by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107438484A CN107438484A (en) | 2017-12-05 |
| CN107438484B true CN107438484B (en) | 2020-08-11 |
Family
ID=57006132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680020546.0A Active CN107438484B (en) | 2015-04-01 | 2016-03-30 | Sodium polyphosphate supported catalyst with improved activity and method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol by using same |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR101706449B1 (en) |
| CN (1) | CN107438484B (en) |
| WO (1) | WO2016159650A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3781222A (en) * | 1970-04-16 | 1973-12-25 | Raffinage Cie Francaise | Dehydration catalysts,particularly for the dehydration of diols |
| CN1052661A (en) * | 1989-08-08 | 1991-07-03 | 联合碳化化学品及塑料有限公司 | Use has the amines catalysis of the metallic polyphosphate condensation catalyst of condensation structure |
| CN101580462A (en) * | 2009-05-08 | 2009-11-18 | 清华大学 | Method for preparing ethyl methyl ketone by dehydrating 2,3-butanediol efficiently |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101298672B1 (en) * | 2012-02-20 | 2013-08-21 | 한국화학연구원 | Fabrication method of 1,3-butadiene from 2,3-butanediol |
| KR101402889B1 (en) * | 2012-11-30 | 2014-06-02 | 지에스칼텍스 주식회사 | Lithium phosphate supported catalyst with improved activity and method of preparing methylethylketone and 1,3-butadiene from 2,3-butanediol using the same |
| KR101410369B1 (en) * | 2012-12-12 | 2014-06-20 | 지에스칼텍스 주식회사 | Silico-metal-phosphate catalyst and preparing method of 1,3-butadiene and methylethylketone using the same |
| KR101472535B1 (en) * | 2013-03-13 | 2014-12-16 | 한국화학연구원 | Fabrication Method of 1,3-Butadiene and Methyl Ethyl Ketone from 2,3-Butanediol |
-
2015
- 2015-04-01 KR KR1020150046430A patent/KR101706449B1/en active IP Right Grant
-
2016
- 2016-03-30 CN CN201680020546.0A patent/CN107438484B/en active Active
- 2016-03-30 WO PCT/KR2016/003249 patent/WO2016159650A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3781222A (en) * | 1970-04-16 | 1973-12-25 | Raffinage Cie Francaise | Dehydration catalysts,particularly for the dehydration of diols |
| CN1052661A (en) * | 1989-08-08 | 1991-07-03 | 联合碳化化学品及塑料有限公司 | Use has the amines catalysis of the metallic polyphosphate condensation catalyst of condensation structure |
| CN101580462A (en) * | 2009-05-08 | 2009-11-18 | 清华大学 | Method for preparing ethyl methyl ketone by dehydrating 2,3-butanediol efficiently |
Non-Patent Citations (1)
| Title |
|---|
| Catalytic Performance and Characterization of Silica Supported Sodium Phosphates for the Dehydration of Methyl Lactate to Methyl Acrylate and Acrylic Acid;Zhiqiang Zhang等;《Ind. Eng. Chem. Res.》;20090923;第48卷;9083-9089 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101706449B1 (en) | 2017-02-15 |
| CN107438484A (en) | 2017-12-05 |
| WO2016159650A1 (en) | 2016-10-06 |
| KR20160118469A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102482177B (en) | Carbohydrate route to para-xylene and terephthalic acid | |
| CN112920139B (en) | Dimorpholinyl diethyl ether and preparation process thereof | |
| CN103922931B (en) | A kind of method of a step catalytically synthesizing glycol ether acetate | |
| CN103143381B (en) | Carbon nitride material immobilized heteropolyacid catalyst and olefin epoxy synthesizing method | |
| JP2015168644A (en) | IMPROVEMENT OF PREPARATION CONDITIONS OF METAL-ADDED MgO-SiO2 CATALYST EFFECTIVE FOR BUTADIENE SYNTHESIS FROM ETHANOL | |
| CN103228601B (en) | Prepare the method for Santosol 360 | |
| CN107438484B (en) | Sodium polyphosphate supported catalyst with improved activity and method for preparing methyl ethyl ketone and 1,3-butadiene from 2,3-butanediol by using same | |
| US6072090A (en) | Olefin hydration process | |
| US3822321A (en) | Method of synthesizing diols | |
| Li et al. | Hydrodeoxygenation of 1, 2-decanediol to produce 1-decanol over Cu/SiO2-Al2O3 catalyst | |
| CN110872208A (en) | Cyclohexanol preparation method by coupling cyclohexane mixture dehydrogenation technology | |
| JPWO2004060843A1 (en) | Method for producing alcohol and / or ketone | |
| TW201914688A (en) | Method for producing ethylene from ethanol raw material having a higher ethanol conversion rate and higher ethylene selectivity | |
| JPWO2013108543A1 (en) | Olefin production method | |
| TW201641479A (en) | Process | |
| JPS6218532B2 (en) | ||
| US8269036B2 (en) | Processes for producing an oxalate by coupling of CO | |
| RU2421441C1 (en) | Single-step method of producing isoprene | |
| US2979510A (en) | Preparation of pyridine | |
| JPH09169688A (en) | Production of isophorone | |
| US6939996B2 (en) | Process for the hydrogenation of alkylaryl ketones | |
| CN103420759B (en) | The production method of propylene | |
| Li et al. | Lacunary Keggin polyoxotungstate as reaction‐controlled phase‐transfer catalyst for catalytic epoxidation of olefins | |
| CN108484353B (en) | Synthetic method of 2, 4-dichloro-5-fluoro (trichloromethyl) benzene | |
| US3205244A (en) | Improved catalytic synthesis of carboxylic acids from olefins, carbon monoxide and water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |